Hydrocarbyl-modified methylaluminoxane cocatalysts for bis-phenylphenoxy metal-ligand complexes

Abstract

Processes of polymerizing olefin monomers. The process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises: an activator; hydrocarbyl-modified methylaluminoxane having less than 25 mole percent trihydrocarbyl aluminum compounds A1R A1 R B1 R C1 based on the total moles of aluminum, where R A1 , R B1 , and R C1 are independently linear (C 1 -C 40 )alkyl, branched (C 1 -C 40 )alkyl, or (C 6 -C 40 )aryl; and one or more metal-ligand complexes according to formula (I):

The invention claimed is: 
     
         1 . A process of polymerizing olefin monomers, the process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises: an activator; hydrocarbyl-modified methylaluminoxane having less than 25 mole percent trialkyl aluminum based on the total moles of aluminum, wherein trialkyl aluminum has a formula of A1R A1 R B1 R C1 , wherein R A1 , R B1 , and R C1  are independently linear (C 1 -C 40 )alkyl, branched (C 1 -C 40 )alkyl, or (C 1 -C 40 )aryl; and one or more metal-ligand complexes comprising a metal-ligand complex according to formula (I): 
       
         
           
           
               
               
           
         
         wherein: 
         M is titanium, zirconium, hafnium, scandium, yttrium, or an element of the lanthanide series of the periodic table; 
         n is 1,2, or 3; 
         each X is a monodentate ligand independently chosen from unsaturated (C 2 -C 50 )hydrocarbon, unsaturated (C 2 -C 50 )heterohydrocarbon, (C 1 -C 50 )hydrocarbyl, (C 6 -C 50 )aryl, (C 6 -C 50 )heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C 4 -C 12 )diene, halogen, —N(R N ) 2 , and —N(R N )COR C , optionally, two X may be linked together; 
         the metal-ligand complex is overall charge-neutral; 
         each Z is independently chosen from —O—, —S—, —N(R N )—, or —P(R P )—; 
         R 1  and R 16  are independently selected from the group consisting of —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, —N═C(R C ) 2 , R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, halogen, radicals having formula (II), radicals having formula (III), and radicals having formula (IV): 
       
       
         
           
           
               
               
           
         
         
           wherein each of R 31-35 , R 41-48 , and R 51-59  is independently chosen from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R N )—, (R C ) 2 NC(O)—, or halogen; 
         
         R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15  are independently selected from —H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, —Si(R C ) 3 , —Ge(R C ) 3 , —P(R P ) 2 , —N(R N ) 2 , —OR C , —SR C , —NO 2 , —CN, —CF 3 , R C S(O)—, R C S(O) 2 —, (R C ) 2 C═N—, R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, and halogen; 
         L is (C 1 -C 40 )hydrocarbylene or (C 2 -C 40 )heterohydrocarbylene; and 
         each R C , R P , and R N  in formula (I) is independently a (C 1 -C 30 )hydrocarbyl, (C 1 -C 30 )heterohydrocarbyl, or —H; 
         wherein the ratio of moles of aluminum in the hydrocarbyl-modified methylaluminoxane to moles of metal in the metal-ligand complex is less than 500. 
       
     
     
         2 . The polymerization process according to  claim 1 , wherein the ratio of moles of aluminum in the hydrocarbyl-modified methylaluminoxane to moles of metal in the metal-ligand complex is from greater than 20 to less than 300. 
     
     
         3 . The polymerization process according to  claim 1 , wherein the hydrocarbyl-modified methylaluminoxane has less than 20 mole percent of trialkyl aluminum based on the total moles of aluminum. 
     
     
         4 . The polymerization process according to  claim 1 , wherein the hydrocarbyl-modified methylaluminoxane has less than 15 mole percent of trialkyl aluminum based on the total moles of aluminum; or wherein the hydrocarbyl-modified methylaluminoxane has less than 10 mole percent of trialkyl aluminum based on the total moles of aluminum. 
     
     
         5 . The polymerization process according to  claim 1 , wherein the hydrocarbyl-modified methylaluminoxane is modified methylaluminoxane. 
     
     
         6 . The polymerization process according to  claim 1 , wherein at least one of R 1  and R 16  is a radical having formula (III). 
     
     
         7 . The polymerization process according to  claim 6 , wherein R 42  and R 47  are (C 1 -C 20 )hydrocarbyl or —Si[(C 1 -C 20 )hydrocarbyl] 3 ; or wherein R 43  and R 46  are (C 1 -C 20 )hydrocarbyl or —Si[(C 1 -C 20 )hydrocarbyl] 3 . 
     
     
         8 . The polymerization process according to  claim 1 , wherein at least one of R 1  and R 16  is a radical having formula (II). 
     
     
         9 . The polymerization process according to  claim 8 , wherein R 32  and R 34  are (C 1 -C 12 )hydrocarbyl or —Si[(C 1 -C 20 )hydrocarbyl] 3 . 
     
     
         10 . The polymerization process according to  claim 1 , wherein at least one of R 1  and R 16  is a radical having formula (IV) and at least two of R 52 , R 53 , R 55 , R 57 , and R 58  are (C 1 -C 20 )hydrocarbyl or —Si[(C 1 -C 20 )hydrocarbyl] 3 . 
     
     
         11 . The polymerization process according to  claim 1 , wherein R 8  and R 9  are independently selected from (C 1 -C 20 )alkyl. 
     
     
         12 . The polymerization process according to  claim 1 , wherein R 8  and R 9  are independently selected from methyl, ethyl, 1-propyl, or 2-propyl. 
     
     
         13 . The polymerization process according to  claim 1 , wherein R 3  and R are (C 1 -C 10 )alkyl. 
     
     
         14 . The polymerization process according to  claim 1 , wherein R 7  and R are halogen. 
     
     
         15 . The polymerization process according to  claim 1 , wherein R 6  and R 11  are tert-butyl. 
     
     
         16 . The polymerization process according to  claim 1 , wherein L is chosen from —CH 2 (CH 2 ) m CH 2 —, wherein m is 1 to 3, —CH 2 Si(R C )(R D )CH 2 —, —CH 2 Ge(R C )(R D )CH 2 —, bis(methylene)cyclohexan-1,2-diyl; —CH 2 CH(R C )CH 2 —, —CH 2 C(R C ) 2 CH 2 —, wherein each R C  in L is (C 1 -C 20 )hydrocarbyl and R D  in L is (C 1 -C 20 )hydrocarbyl. 
     
     
         17 . The polymerization process according to  claim 1 , wherein M is zirconium or hafnium. 
     
     
         18 . The polymerization process according to  claim 1 , wherein the olefin monomer is (C 3 -C 20 )α-olefin. 
     
     
         19 . The polymerization process according to  claim 1 , wherein the olefin monomer is cyclic olefin. 
     
     
         20 . The polymerization process according to  claim 1 , wherein the olefin monomer is not (C 3 -C 20 )α-olefin.